Synthesis of ethyl benzene



Sept. 18, 1945. P. H. BLANDING l 385,187

. SYNTHESIS OF ETHYL BENZENE Filed Aug. 22, 1942 HG2. rino/va 75# mlm,

Patented Sept. 18, 1945 SYNTHESIS F ETHYL BENZENE Forrest H. Blanding, Elizabeth, N .-J assignor to Standard Oil Development Company, a corporation ot Delaware Application August 22, 1942, Serial No. 455,702

3 Claims.

The present invention vrelates to the ethylation of aromatic hydrocarbons and in particular, ethylation of benzene by means of Friedel-Crafts type catalyst, in particular the aluminum halides such as aluminum chloride, while carrying out the reaction under reaction conditions and in the presence of promotional amounts of halogencontaining compounds.

In the ethylation of aromatic hydrocarbons such as benzene, it is customary to employ cat alysts of the Friedel-Crafts type such as, for example, zinc chloride, aluminum chloride, aluminum bromide, iron chloride and the like, in con- Junction with one 'or more promoters such as, for example, hydrogen, chlorine, bromine, hydrogen chloride, hydrogen bromide, carbon tetrachloride, chloroform, the lower alkyl halides such as, for example, methyl, ethyl, propyl, butyl chlorides and bromides and the like. Small amounts of water have also been employed for promoting this reaction and therefore some superatmospheric pressure was sometimes used to maintain the liquid phase operation. However, the diillculties encountered in liquid phase operation have made it expedient to consider and 'perfect a process employing vapor phase operation in which a solid bed of catalyst, for example aluminum chloride impregnated or deposited upon suitable carriers, either reactive to some extentv or inert, is employed and in which aromatic hydrocarbon vapors together with promoter are allowed to pass through and in intimate contact with the bed under reaction conditions.

'I'he present invention is concerned with the yapor phase ethylation of benzene. The catalyst employed is prepared by lmpregnating aluminum chloride or other suitable Friedel-Crafts type catalyst on or into highly absorbent carrier substances to be more fully hereinafter described. In preparing these catalyst masses it has been found desirable, and in fact essential, to a smooth and economical operation obviating the necessity for frequent plant shutdowns, to impregnate or sorb on or in the carrier substance only suiilcient aluminum chloride as will be tenaciously held in the pores of the carrier substance under the conditions of ethylation obtaining. This is expedient by reason of the fact that aluminum chloride vapors when present to any great extent in the reacted eluent from the ethylation reactor tend to condense and deposit in'valves, pipes, stills and the like, necessitating the removal and shutdown for cleaning of these various pieces of equipment. Although it is preferred to make up the catalyst mass so that only tenaciously held ythe carrier, in which case provision is made for the removal of the excess aluminum chloride vapors by their sorption in another mass of carrier or the like.

The present invention is concerned with the .maintenance of the effective usefulness of the catalyst mass over a longer period of time than has heretofore been possible. This may be accomplished by introducing either intermittently, continuously, or.continuously-intermittently, vapors of aluminum chloride or other suitable Friedel-Crafts type catalyst into the catalyst mass which is catalyzing ethylation reactions. This may be accomplished in a number of ways to be more fully hereinafter disclosed. It has been found, however, that particularly with respect to the carrier, 'the effective life thereof is materially lengthened, and from the economics of the process a commercial plant may be eiliciently operated by employing the improvements herein described.

It is an object of the present invention to maintain a longer effective usefulness with incident high catalytic activity of an ethylation catalyst bed. particularly in connection with its use in the vapor phase ethylation of benzene. It is a further object of the present invention to cari'y out a continuous commercial process for the production of high yields of ethyl benzene from the corresponding ethylene and benzene as economically as possible and to avoid the necessity for shutdowns due to excessive degradation ofthe catalyst bed and/orplugging of the valves and lines with aluminum chloride deposited thereon and therein which was caused by the fact that excessive amounts of aluminum chloride were vaporized or dissolved in the eilluent coming from the ethylation reaction zone.

It is a further object of the invention to add and substantially completely sorb aluminum chloride or other Friedel-Crafts type catalysts in vapor form to a catalyst bed to lengthen itseffective catalyst life, and yet to add these vapors in such a way as to prevent substantial loss of aluminum chloride from said bed through vaporization or solution in the reacted eiliuent coming therefrom. It is a further object of the invention to maintain a substantially uniform distribution of aluminum halides or other Friedelg Crafts type catalyst, particularly aluminum chloride, throughout the sorbent carrier mass. It is a further object of the invention to maintain a maximum life for the sorptive carriers employed in making up the ethylation catalyst bed.

In order to accomplish these objects as well as others which will hereinafter appear upon a fuller and more complete understanding of the invention, the following description and explana Vand the like, and the mixture heated to an elevated temperature, depending upon the particular carrier employed, suiilcient to complete the sublimation of the less tenacious'ly held aluminum chloride, for example, followed by a removal of all excess or extraneoushr and loosely held aluminum chloride from-the porous mass.Y The temperature under which this may be carried out is generally from 50 F. to 100 F. in excess of the highest temperature to be employed in the ethylation reaction in which the catalyst mass will be employed.

Still another method of preparing the catalyst bed is to take a suitable highly sorbent carrier of the type heretofore specified and to independently sublime or vaporize aluminum chloride and by means of a suitable carrier gas or vapor, impregnate the porous carrier with the aluminum that the carrier is substantially completely saturated with the aluminum chloride vapors andhighest temperature to be contemplated for use in the subsequent ethylation reaction zone. Generally a temperature between about 275 to 350 F. is employed where vapor phase ethylation of benzene is contemplated. In prepmng acatalyst for ethylation of benzene, temperatures of from 250 to 450 F. are generally desirable for the impregnation step. The amount of aluminum -chloride contained in the pores of sorptive carriers varies depending upon the particular sorptive carrier employed, but in general it will be found-to range between about 8% and about 15% by weight of4 the catalyst mass. The aluminum chloride vapor carriers employed may be of widely'varying characteristics but it is only necessary that they be gases at or above|- the sublimation temperatures employed for the aluminum chloride and that they be relatively inert with regard to the aluminum chloride under the conditions employed for iml-V pregnation of the aluminumv chloride on porous chloride until such time and in such amounts so water is given off under the ethylation conditions to which the carrier subsequently is subiected. The bauxite may be dried and calcined by any of the customary methods employed. The particular calcined bauxite which is preferred in the present invention is Porocel which has been previously heated for a period of about 18 hours at a, temperature between about 950 and about 1000 F. As previously stated, one of the methods of preparing the catalyst is simply to charge the ethylation reactor with the dehydrated Porocel alone and to impregnate and sorb aluminum chloride directly therein, or the Porocel may be impregnated with anhydrous aluminum chloride in a separate and independent step and the resultant catalyst may be charged into the ethylation reaction zone.

The feed stock employed in conjunction with this catalyst is benzene which is also useful as a carrier medium for the introduction of further quantities of aluminum chloride into the catalyst bed simultaneously with the ethylation reaction.

The ethylation reaction is carried out in the presence of suitable promoters, as heretofore mentioned. These are customarily employed in amounts ranging between about 1% and about 18% based on the quantity of benzene and ethylene. although higher amounts may be employed without deleterious effects on the ethylation reaction. Oftentimes it is desirable to employ higher amounts of promoter, particularly where these promoters such as chlorine, hydrogen chloride and/or hydrogen, serve as the carrier medium in introducing the further quantities of aluminum chloride into the. catalyst mass since by regulating the amount of carrier gas it is possible to regulate the amount of' aluminum chloride being introduced into the catalyst bed.

carriers. Such gases as benzene, nitrogen, air,

carbon dioxide, hydrogen, chlorine, hydrogen chloride, methane, ethane," propane, normal butane or isobutane and the like may be, eithersingly or in admixture with one another, employed for this purpose. Y The impregnation of the porous carriers may also be carried out by dissolving aluminum chloride in a liquid such as butane or benzene, and adding to the porous carriers.

One of the particularly desirable carriers which Times of contact vary, particularly in continuous umts, but in general the time of contact will be between 0.2 and about 3 liquid volumes of feed stock per volume of catalyst per hour (30 to 600 seconds) and the temperature maintained in the reaction zone varies between 250 and 400 F., preferably between 275 to 350 F., while maintaining a pressure between atmospheric and 350 lbs. per square inch. When ethyl benzene and polymer are to be separated from hydrogen chloride, ethylene, and benzene in a stripping tower and the hydrogen chloride, ethylene, and benzene recycled to the reaction zone, a maximum pressure that will permit vapor phase operation is used.

These various reaction conditions are necessarily correlated with respect to one another for in the ethylation of benzenes where the boiling points of benzene and ethyl benzene are 176 and 277 F. respectively, the reaction temperatures may be varied from 275 to 350 F. Furthermore, the temperatures may be increased to some extent as the catalyst mass becomes degraded beyond a point where additional introduction of aluminum chloride to the catalyst mass does not maintain its activity. In such a oase the temperature is raised and the reaction conditions are made slightly more drastic for a given feed stock in order to attain the greatest yield of desired product per unit of weight of aluminum chloride charged to the catalyst mass.

It has also been foundexpedient in carrying outa commercial operation of this type, to subject the feed stocks, ethylene and benzene, to a pretreatment with a suitable agent for the removal of =wat/er if it is present in objectionable quantities. For example, activated charcoal, clay or bauxite may be employed, as well as other substances commonly employed in such treatments. 'Ihis pretreatment is best carried out in liquid phase operation in which the feed stock is maintained in liquid state through the clay filter treatment.. 'lhe clay filter treatment of course may be omitted if the feed stock does-not contain any appreciable amounts of water to cause any appreciable disurbance of the activity of the aluminum chloride in the subsequent ethylation reaction.'

The feed stock is subjected to sufficient heating to vaporize the same under the pressures obtaining and its temperature is subsequently adjusted in accordance with a number of factors. In the first place, the temperature is generally adjusted to that desired to-be maintained in the reaction. zone. 'I'his may be accomplished in two ways. In

the rst method, benzene is heated to the desired e reaction temperature and passed into a chamber containing granular or comminuted aluminum chloride with such velocity as to vaporize'and pick up the desired amount of aluminum chloride, and

this aluminum chlorideis introduced into the vreaction zone. However, a second method is also contemplated in which only a portion of the benethylation reaction zone with a cooling` or heating thereof in order to adjust the temperatures to the desired reaction temperatures. Cool liquid benzene may be added to the aluminum chloride in a drum and then vaporized and the vapors passed to the ethylation reaction zone. -Still a further embodiment of the process of the invention resides in admixing a portion of the promoter such as, for example, hydrogen chloride and/ or chlorine and/or hydrogen with benzene and conducting the mixture in whole or in part, as before, through the aluminum lchloride pick-up drum where the aluminum chloride vapors are carried bythese gases and vapors to the ethylation reaction zone for sorption in the catalyst mass under the ethylation reaction conditions. It has been found that once the ethylation catalyst mass has attained a composition of aluminum chloride therein between about 8% by weight and about 20% by weight, depending upon the carrier used, it is sumcient in order to maintain its activity to have the vapors entering the reaction zone contain between about 0.005% and about 0.1% vby weight of aluminumrchloride based on the feed, preferably between about 0.01% and about 0.05% by weight. Actually, there is no necessity for limiting the amount of aluminum chloride vapors entering the ethylation catalyst bed except that the amount should not exceed that which can be substantially completely sorbed. The upper limit, therefore, is really fixed by the capacity of the actors.

ethylation catalyst bed which tend to eventually lead to the difficulties heretofore mentioned such as line pluggingvalve sticking, etc. Liquid benzene at low (room) temperature could be used to pick up the aluminum chloride from the aluminum chloride pick-up drum and then be vaporized and admixed with .the prom'oter in the reaction zone.

Stillother variations of the method of introducing the aluminiun chloride vapors into the ethylation catalyst-bed are employed. The promoter such as, for example, hydrogen chloride, either alone or in conjunction with molecular hydrogen, may be used exclusively for picking up the aluminum chloride vapors and introducing them into the reaction zone, or these promoters maybe introduced in the reaction zone admixed with that portion of the benzene which does not go through the aluminum chloride pick-up chamber.

No special type of apparatus construction is necessary in carrying out the process of the present invention. It is sufficient that equipment which has customarily been employed for vapor under superatmospheric pressure the vessels should be of the ordinary pressure type. The reactors may be a, single reactor or a plurality of reactors arranged in series or parallel so that the"V feed stock and the unit may be continuously onstream even through one or more reactors may be voff-stream for removal of spent catalyst or its -feed stock at the bottom thereof and allow it to flow through the catalyst mass upwardly and emerge from the reactor from the top. However,

downilow operation is also possible. 'Multiple reactors may be employed, either in series or paral1el. When it becomes necessary to discontinue order to maintain their temperature, and consorbentt carrier to take up the aluminum chloride vapors. It is generally not desirable to introduce aluminum chloride vapors in amounts over and above that which will be substantially completely sorbed. The reacted vapors leaving the ethylation zone should contain not more than about 0.004% by weight, based on the hydrocarbon feed, of aluminum chloride since under continuous 'operation higher amounts represent unsorbed and loosely held aluminum chloride contained in the venient heat interchangers may be employed, particularly with respect to the introduction of the reacted eluent into the promoter stripping tower and the removal of the stripped reacted mixture therefrom.

Not only may the catalyst mass b e maintained so far as its activity is concerned in the manner heretofore described, but it may likewise be prepared or regenerated in the same manner, that is, i

by the use of normal butane, for example, and/or hydrogen chloride or chlorine vapors and gases as carrier media for vaporized aluminum chloride which is introduced to reimpregnate or impregnate the Porocel or other absorbent carrier employed. In regenerating the catalyst mass it is suggested to remove substantially all carbonaceous impurities contained in the pores thereof by combustion using air or free oxygen, either undiluted or diluted, with an inert gas such as nitrogen, carbon dioxide, etc., to burn the carbonaceous material from the pores. It is then possible to reimpregnate the poresof the carrier with aluminum chloride vapors as previously described.

ySince the process may be carried out A preferred type or apparatus is illustrated by the drawing in which numeral I indicates the pipe provided with pump 2 through which benzene is passed into the reactor 1. Numeral 3 indicates the pipe through which ethylene is passed into pipe 4, where together with makeup hydrogen chloride promoter introduced by means of pipe 5 it is passed through heater 6 and into the lower part'of the reactor 1. 'I'he benzene pipe i is also provided with a heater 8 before it is passed into the reactor 1. A by-pass'pipe 9 is provided with valve I0 connected torpipe I which passes through an aluminum chloride drum Il where it picks up aluminum chloride. It is then passed to pipe I2 through heater 8 into pipe i. Another pipe Il provided with a heater I4, may be used to pass hydrogen or any other inert gas as a carrier kfor aluminum chloride into pipe l and through aluminum chloride drum II into pipe I. The reactor contains aluminum chloride impregnated on Porocel or other carrier. The two react= ing materials, benzene or ethylene, are passed through` the beds of catalyst and removed from reactor 1 by means of pipe I5, condensed in condenser IS and by means of pump I1 passed into distillation column I8. In the distillation column hydrogen chloride, unreacted benzene and ethylene are removed by means of pipe I9 and may be recycled to the bottom of the reactor by means of pipes 20 and 4 or passed to pipe 2i to knockout drum 22 where the inert low` boiling gases such asnitrogen, hydrogen and methane are removed through pipe 23 and the benzene recycled through pipe Zito pipe I. The ethyl benzene formed and higher boiling compounds are removed from distillation column I8 by means o! pipe 25 and passed to a second distillation column 26 where the ethyl benzene product is obtained overhead throughrpip'e 21 and the polyethyl benzenes polymer removed as bottoms by means of pipe 28.

Example Twelve parts of dried benzeneare passed at room temperature through chamber cni'in- 5 and ethylene with a catalyst mass consisting of ing aluminum chloride, heated to 300 F., and passed to the bottom of a reactor containing 'a catalyst consisting of 12 wt. per cent of aluminum chloride impregnated on 88 wt. per centv Porocel.

seems? i One part of anhydrous hydrogen 'chloride and 0 parts of dry ethylene are also heated to 300 E. and admitted to the bottom of the same reactor. Also the reactor is maintained at about 5 pounds per square inch pressure or less. The product gases coming from the reactor are cooled and fed to a fractionatlng column which separates the. ethyl benzene and higher boiling polymers from the benzene, ethylene, and hydrogen chloride excess. The excess benzene, ethylene (a small amount) and hydrogen chloride, along with make-up hydrogen chloride and more ethylene, is recycled to the reactor. The ethyl benzene is separated from higher boiling alkylated benzenes and polymers in another fractionating column.

I claim:

1. 'I'he process of ethylialngbenzene which comprises contacting ethylene and benzene in the vapor phase, at a temperature ranging from 250 F. to 400 F. in the presence of a porous sorptive carrier containing impregnated therein and thereon 8 to 20% oi aluminum haliderby weight of the catalyst mass while simultaneously introducing into the catalyst mass aluminum halide vapors carried by the hydrocarbon feed mixture.

2. A process of ethylizing benzene which coml prises contacting ethyleneand benzene in the Avapor phase at a temperature ranging from 250 F. to 400 E., in the presence of a porous sorptive carrier containing impregnated therein and thereon 8 to 15% of aluminum chloride by weight oi the catalyst mass while simultaneously introducing into lthe catalyst mass 0.01 to 0.05% aluminum halide vapors based on the hydrocarbon feed.

3. The process of ethyliz'ing benzene which comprises contacting liquid benzene maintained below its boiling point with aluminum chloride,

40 heating the benzene with the dissolved aluminum chloride at a temperature between 275 F. and 350 F., at a pressure not over 5 pounds per square inch, and contacting the hot benzene with the dissolved aluminum chloride, hydrogen chloride 8% to 15% of aluminum chloride by weight of the catalyst mass impregnated on a highly absorbent carrier substance. FORRBT H. BLANDIVNG. 

